JPH08302175A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant resin composition excellent in flame retardancy, heat resistance and impact resistance with excellent balance among physical properties and useful for applications in, e.g. electronic and electrical products and office automation machinery and as a material for various parts. CONSTITUTION: This flame-retardant resin composition comprises 100 pts.wt. resin component consisting of 1-99wt.% polycarbonate resin (A), 1-50wt.% graft copolymer (B) and 0-98wt.% thermoplastic resin (C) other than the components A and B and 1-50 pts.wt. phosphorus compound (D), wherein the total content of sodium and potassium present in the copolymer B is at most 200ppm, the content of magnesium therein is at most 15ppm, and the content of calcium therein is at most 1,000ppm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition. More specifically, the present invention relates to a flame-retardant resin composition containing a polycarbonate resin having improved flame retardancy, heat resistance and impact resistance without using a brominated flame retardant and a graft copolymer as essential components.

[0002]

2. Description of the Related Art Conventionally, polycarbonate resin and AB
A resin composition containing S resin as an essential component (hereinafter referred to as PC / A
BS alloy) is used in a wide range of applications because of its excellent balance of physical properties and good moldability. However, depending on the application, it is necessary to have flame retardancy. For example, it may be used as an electric / electronic device component, OA device, household product, or building material. PC
As a method for imparting flame retardancy to / ABS alloy, a brominated flame retardant is generally added, but a part of the brominated flame retardant is decomposed during kneading and molding, and free bromine gas or bromine compound is generated. It produces and corrodes the surfaces of cylinders, screws, and molds of kneading machines and injection molding machines, and in the field of electrical and electronic equipment parts, corrodes metal parts and causes contact failures and conduction failures. Furthermore, it has been pointed out that some bromine-based flame retardants contain extremely toxic brominated dibenzodioxin, dibenzofuran, etc., even though they are extremely small at the time of molding and burning, which not only worsens the working environment of the workplace. However, when incinerating a resin product containing such a brominated flame retardant, there is a sufficient risk of contaminating nature. As a method for eliminating such a defect, JP-A-2-32154 proposes to add a phosphorus compound or the like to the PC / ABS alloy instead of the brominated flame retardant. However, in order to achieve a high flame retardancy level, it is necessary to add a large amount of these phosphorus compounds, and the mechanical properties such as heat resistance and impact resistance of PC / ABS alloy are impaired. Had.

[0003]

The present invention has been made against the background of the above-mentioned problems of the prior art. The object of the present invention is to prevent the generation of harmful substances during molding and combustion. Moreover, it is to provide a flame-retardant resin composition containing a polycarbonate resin and a graft copolymer, which are excellent in flame retardancy, heat resistance, and impact resistance.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that in a resin composition containing a polycarbonate resin, a graft copolymer and a phosphorus compound, the graft copolymer It has been found that, when the residual amount of sodium, potassium, magnesium and calcium in the coalescence is reduced, surprisingly, the flame retardancy of the resin composition is improved. That is, among the impurities in the graft copolymer, silicon, aluminum, iron, residual sulfuric acid / hydrochloric acid, etc. do not significantly affect the flame retardancy, but alkali metals and alkaline earth metals have a large effect on the flame retardancy. I found that. As a result, the addition amount of the phosphorus compound can be reduced, so that a flame-retardant resin composition having excellent heat resistance and impact resistance and containing no brominated flame retardant can be obtained. It was done. That is, the present invention provides (1) (A) 1 to 99% by weight of a polycarbonate resin, and (B) a graft copolymer 1
In a composition containing 1 to 50 parts by weight of (D) a phosphorus compound per 100 parts by weight of a resin component consisting of 0 to 50% by weight and (C) 0 to 98% by weight of a thermoplastic resin other than (A) and (B). , The total concentration of sodium and potassium present in the graft copolymer is 200 ppm or less, the concentration of magnesium is 150 ppm or less, and the concentration of calcium is 1000 ppm or less, a flame-retardant resin composition, (2 ) (A) Polycarbonate resin 1 to 99% by weight, (B) Graft copolymer 1 to 50% by weight, (C)
(D) Phosphorus compound 1 per 100 parts by weight of a resin component consisting of 0 to 98% by weight of a thermoplastic resin other than (A) and (B)
.About.50 parts by weight and (E) at least one selected from silicone, fluorine resin, and phenol resin.
In a composition containing 01 to 30 parts by weight, the total concentration of sodium and potassium present in the graft copolymer is 200 ppm or less, and the concentration of magnesium is 150.
The flame-retardant resin composition is characterized by having a concentration of ppm or less and a calcium concentration of 1000 ppm or less.

The present invention will be described in more detail below. The (A) polycarbonate resin used in the present invention can be produced by reacting a dihydric phenol with phosgene or a carbonic acid diester. Examples of the dihydric phenol include hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl). Examples thereof include sulfone, bis (4-hydroxyphenyl) ketone, and the like, or a nuclear alkylated derivative thereof, preferably bisphenols, particularly preferably 2,
It is 2-bis (4-hydroxyphenyl) propane.
It may be a homopolymer of these dihydric phenols, a copolymer of two or more kinds, or a blended product thereof. If necessary, a branching agent (usually a polyfunctional aromatic compound) and a randomly branched polycarbonate obtained by reacting a dihydric phenol with phosgene or a carbonic acid diester are also included. These polyfunctional aromatic compounds contain at least three functional groups such as carboxy, hydroxy, carboxylic acid anhydrides, haloformyl and combinations thereof. Specific examples of the branching agent include trimellitic anhydride, trimellitic acid, and 4
-Chloroformylphthalic anhydride, pyromellitic acid, phloroglucin, gallic acid, propyl gallate, mellitic acid,
Examples include trimesic acid and benzophenone tetracarboxylic acid.

The (B) graft copolymer used in the present invention is an elastomer 10 having a glass transition temperature of 10 ° C. or lower.
In the presence of 0 part by weight, a monomer 5 to 2000 comprising at least one kind of aromatic vinyl compound, (meth) acrylic acid ester, vinyl cyanide compound, maleimide compound, etc.
It can be obtained by (co) polymerizing parts by weight. Further, an aromatic vinyl compound having a functional group that reacts with 100 parts by weight of an elastomer having an epoxy group, an amino group, an acid anhydride group or the like and a glass transition temperature of 10 ° C. or less, and a (meth) acrylic acid ester, It can also be obtained by extrusion reaction with 10 to 2000 parts by weight of a (co) polymer containing at least one kind of vinyl cyanide compound, maleimide compound and the like.

As the elastomer having a glass transition temperature of 10 ° C. or lower, for example, polybutadiene, butadiene-styrene copolymer, butadiene-styrene block copolymer, hydrogenated butadiene-styrene block copolymer,
Butadiene rubber such as butadiene-acrylonitrile copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, isobutylene-isoprene copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer Examples thereof include polymers, polyurethane rubbers, polyamide rubbers, silicone rubbers and the like. Further, a composite rubber composed of silicone rubber and acrylic rubber or a composite rubber composed of butadiene rubber and acrylic rubber can be used. In the present invention, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene (diene component) copolymer, silicone rubber and the like are preferably used.

Examples of the aromatic vinyl compound which can be used in the (B) graft copolymer of the present invention include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, hydroxystyrene, halostyrene, sodium styrenesulfonate and the like. Preferably, styrene, α-
It is methylstyrene. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and the like, preferably methyl methacrylate and the like. Used. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and fumaronitrile, and acrylonitrile is preferably used.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (Alkyl-substituted phenyl) maleimide and the like can be mentioned, with preference given to N-phenylmaleimide and maleimide. Examples of the unsaturated (di) carboxylic acid (anhydride) include acrylic acid, methacrylic acid, itaconic acid, monomethyl itaconic acid, maleic acid (anhydrous), monomethyl maleate, fumaric acid, and the like, preferably maleic anhydride. , Acrylic acid,
Methacrylic acid or the like is used.

The proportion of the elastomer having a glass transition temperature of 10 ° C. or less in the graft copolymer is preferably in the range of 5 to 95% by weight, more preferably 10 to 95% by weight.
It is in the range of 90% by weight. If the proportion of the rubber-like polymer is less than 5% by weight, the impact resistance is not sufficient, and if it exceeds 95% by weight, the graft ratio, the surface gloss of the resin, the moldability and the flame retardancy are deteriorated. The graft ratio of the graft copolymer is preferably 5 to 150% by weight, more preferably 10 to
It is 120% by weight. When the graft ratio is less than 5% by weight, sufficient impact resistance cannot be obtained, and when it exceeds 150% by weight, dripping tends to occur during combustion.

It is also possible to use a core / shell type copolymer as the (B) graft copolymer. In this case, the core includes the above rubbery polymers such as polybutadiene, polyisoprene, acrylic rubber, and composite rubber composed of silicone rubber and acrylic rubber. The shell-constituting substance preferably comprises a copolymer obtained from a mixture of the aromatic vinyl compound and the (meth) acrylic acid ester, a polymer obtained from only the (meth) acrylic acid ester, etc. Cross-linking monomers such as diacrylate, butylene dimethacrylate, trimethylolpropane trimethacrylate, vinyl acrylate, vinyl methacrylate, diallyl phthalate, divinylbenzene, trivinylbenzene can be further used in combination, but are not limited thereto. Not something.

Specific examples of the particularly preferable graft copolymer used in the present invention are as follows: ABS graft copolymer, AES graft copolymer, AAS graft copolymer, MBS core / shell type copolymer. Examples thereof include copolymers having a composite rubber composed of silicone and acrylic rubber as a core and polymethylmethacrylate as a shell.

The total concentration of sodium and potassium present in the graft copolymer used in the present invention is 200 pp.
m or less, and the concentration of magnesium is 150 ppm or less,
And the concentration of calcium is 1000 ppm or less, preferably the total concentration of sodium and potassium is 180 p
pm or less, the concentration of magnesium is 120 ppm or less, and the concentration of calcium is 800 ppm, and particularly preferably, the total concentration of sodium and potassium is 150.
It is important that the concentration of ppm or less, the concentration of magnesium is 100 ppm or less, and the concentration of calcium is 700 ppm or less. The total concentration of sodium and potassium is 2
The concentration of magnesium exceeds 150ppm, and the magnesium concentration is 150p
If any of the values exceeds pm or the concentration of calcium exceeds 1000 ppm, the flame retardancy of the resin composition decreases, so more phosphorus compounds must be added, As a result, heat resistance or impact resistance is impaired, which is not preferable.

The method for producing the graft copolymer is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and reaction in an extruder can be used. In the case of emulsion polymerization, there is an advantage that it is easy to control the rubber particle size, but impurities such as sodium, potassium, magnesium, and calcium tend to remain, so the type and amount of latex precipitant, addition conditions and washing conditions are optimized. It is necessary. Specifically, it is preferable to avoid precipitation with only an alkali metal salt or an alkaline earth metal salt, and to combine with an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, formic acid or acetic acid, or to precipitate only with an acid.

The concentrations of sodium, potassium, magnesium and calcium in the graft copolymer can be quantified by a known analysis method. For example, potassium and calcium can be quantified by energy dispersive or wavelength dispersive X-ray spectroscopy, and sodium and magnesium can be quantified by ashing and then atomic absorption spectrometry, emission spectrometry or ICP emission spectrometry.

A copolymer obtained by copolymerizing a monomer containing a compound as an essential component, polyester, polyarylate,
Examples thereof include polyamide and polyphenylene oxide.
The ratio of the monomers of the copolymer obtained by copolymerizing a monomer containing an aromatic vinyl compound as an essential component is as follows: aromatic vinyl compound / vinyl cyanide compound, (meth) acrylic acid ester, maleimide compound , At least one monomer selected from unsaturated (di) carboxylic acid (anhydride) and the like = 10/9
0 to 99/1 (weight ratio), particularly preferably 15/85
˜95 / 5 (weight ratio). The aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic acid ester, maleimide compound, and unsaturated (di) carboxylic acid (anhydride) are those exemplified in the (B) graft copolymer. Of course, any of these monomers may be used alone or in combination of two or more. There are no particular restrictions on the production method of these copolymers, bulk polymerization, solution polymerization, suspension polymerization,
A known method such as emulsion polymerization can be used.

Examples of polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polycyclohexane dimethylene terephthalate.
As polyarylate, bisphenol A or 4,4 '
-Aromatic polyesters synthesized from bisphenols such as dihydroxy-diphenyl ether and dibasic acids such as isophthalic acid and terephthalic acid or derivatives thereof, p-hydroxybenzoic acid / biphenol / terephthalic acid, p-hydroxybenzoic acid / 6-hydroxy- Liquid crystalline polyesters such as 2-naphthalenecarboxylic acid / terephthalic acid and p-hydroxybenzoic acid / polybutylene terephthalate may be used. As polyamide, 6-nylon, 6,
Aliphatic nylons such as 6-nylon, 4,6-nylon and 10-nylon and metaxylylenediamine / adipic acid, polyphthalamide, hexamethylenediamine / terephthalic acid / caprolactam, hexamethylenediamine /
Aromatic nylons such as terephthalic acid / isophthalic acid, hexamethylenediamine / terephthalic acid / adipic acid and the like can be mentioned. Examples of the polyphenylene oxide include poly (2,6-dimethyl-1,4-phenylene) ether,
Examples thereof include a 2,6-dimethyl-1,4-phenyl / 2,3,6-trimethyl-1,4-phenol copolymer and a graft copolymer obtained by graft-polymerizing styrene to the former two.

Preferred thermoplastic resins other than (C) (A) and (B) are α-methylstyrene / acrylonitrile copolymers, styrene / acrylonitrile copolymers, styrene / acrylonitrile / methyl methacrylate copolymers, Styrene / N-phenylmaleimide copolymer, styrene / N-phenylmaleimide / acrylonitrile copolymer, styrene / N-phenylmaleimide / maleic anhydride copolymer, polyethylene terephthalate,
They are polybutylene terephthalate, polyarylate composed of bisphenol A / phthalic acid, poly (2,6-dimethyl-1,4-phenylene) ether, and polyamide composed of metaxylene diamine / adipic acid.

In the present invention, the blending ratio of the (A) polycarbonate resin, (B) graft copolymer and (C) thermoplastic resin other than (A) and (B) is as follows:
Component (B): Component (C) = 1 to 99: 1 to 5: 0 to 9
8% by weight, preferably 3 to 97: 2 to 40: 0 to 95
% By weight, particularly preferably 5 to 95: 3 to 30: 0 to 9
0% by weight. If the compounding ratio of the (A) polycarbonate resin is less than 1% by weight, the flame retardancy and impact resistance will deteriorate, while if it exceeds 99% by weight, the moldability will decrease and the impact strength will depend on the thickness. The disadvantage is that the property becomes too large. If the blending ratio of the (B) graft copolymer is less than 1% by weight, the impact strength is insufficient, and conversely, if it exceeds 50% by weight, the disadvantages of lowering the flame retardancy and heat resistance become remarkable. The moldability and / or heat resistance can be improved as the blending ratio of the thermoplastic resin other than (C), (A) and (B) is increased, but if it exceeds 98% by weight, the impact strength is lowered. appear.

In the present invention, (A) a polycarbonate resin, (B) a graft copolymer, and (C) (A), if necessary, within a range that does not impair physical properties such as flame retardancy and impact resistance.
Also, a thermoplastic resin other than the thermoplastic resins other than (B) can be contained. Representative examples among them are (modified) polyethylene, (modified) polypropylene, (modified) ethylene / propylene copolymer resin, polymethylpentene, polyphenylene sulfide, polyacetal, polyetheresteramide, polyetherimide. , Polyetheretherketone, polymethylmethacrylate and the like. These resins can be used in combination of two or more kinds.

The phosphorus compound (D) used in the present invention is not particularly limited as long as it is a compound having a phosphorus atom.
Phosphoric acid ester, phosphorous acid ester, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate,
Examples include phosphazene compounds and red phosphorus,
An organic phosphorus compound represented by the general formula (I) is preferably used.

Embedded image (In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or an organic group, except when R ₁ = R ₂ = R ₃ = H. X represents a divalent or higher valent organic group. , Y is an oxygen source or a sulfur atom, Z is an alkoxy group or a mercapto group, p is 0 or 1, q is an integer of 1 to 30, r is an integer of 0 or more, and n is 0 or 1. However, the present invention is not limited to these.) In the above formula, examples of the organic group include an alkyl group which may be substituted or not, a cycloalkyl group and an aryl group. When it is substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, and the like, and a group in which these substituents are combined (for example, an arylalkoxyalkyl group) or these substituents are oxygen. A group in which an atom, a sulfur atom, a nitrogen atom or the like is bonded and combined (eg, an arylsulfonylaryl group) may be used as a substituent. Further, the divalent or higher valent organic group, from the above organic groups,
It means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom. Examples include alkylene groups, and preferably (substituted) phenylene groups, and those derived from polynuclear phenols such as bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], dihydroxydiphenyl, p, p′-dihydroxydiphenylsulfone, dihydroxynaphthalene, Bis (4-hydroxyphenyl) sulfide, bis (4-
Examples thereof include hydroxyphenyl) sulfone and bis (4-hydroxyphenyl) ketone.

Illustrating these phosphorus compounds, examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate. , Trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate xylenyldiphenylphosphate, diphenyl (2-ethylhexyl) ) Phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresyl phosphate Over, dibutyl phosphate,
Monobutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-
2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and the like, and condensates thereof, such as resorcinol bis (diphenylphosphetoresorcinol bis (dicresyl phosphate), resorcinol bis (dixylenyl phosphate), hydroquinone bis (diphenyl phosphate). ), Hydroquinone bis (dicresyl phosphate), hydroquinone bis (dixylenyl phosphate), biphenol bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate), and other bisphosphates and poly Examples include phosphate oligomers.

A hydroxyl group-containing aromatic phosphate ester containing one or more phenolic hydroxyl groups in triphenyl phosphate, tricresyl phosphate, condensed phosphate ester thereof or the like can also be used as the phosphorus compound. . Examples of the hydroxyl group-containing aromatic phosphate ester include diphenyl resorcinol phosphate, phenyl diresorcinol phosphate, dicresyl resorcinol phosphate, and the like.

Examples of the phosphite include trimethylphosphite, triethylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite, tributoxyethylphosphite, trioleylphosphite, triphenylphosphite, tricresylphosphite. Fight, trixylenyl phosphite, tris (isopropylphenyl) phosphite, trisnonylphenyl phosphite, tris (o-phenylphenyl) phosphite, tris (p-phenylphenyl) phosphite,
Trinaphthyl phosphite, cresyl diphenyl phosphite, xylenyl diphenyl phosphite, diphenyl (2-ethylhexyl) phosphite, di (isopropylphenyl) phenyl phosphite, o-phenyl phenyl dicresyl phosphite, dibutyl phosphite, mono Examples thereof include butyl phosphite, di-2-ethylhexyl phosphite, monoisodecyl phosphite, and condensation products thereof.

In the present invention, a phosphoric acid ester is preferably used as the organic phosphorus compound, and among them, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresyl diphenyl phosphate, xyle is particularly preferable. Examples thereof include monophosphates such as nildiphenyl phosphate and di (isopropylphenyl) phenyl phosphate, and bisphosphates such as resorcinol bis (diphenyl phosphate) and bisphenol A bis (dicresyl phosphate). These phosphorus compounds may be used alone or in combination of two or more.

The blending amount of these phosphorus compounds is (A) polycarbonate resin, (B) graft copolymer, (C)
1 to 50 parts by weight, and preferably 3 to 100 parts by weight of a resin component made of a thermoplastic resin other than (A) and (B).
40 parts by weight, more preferably 5 to 30 parts by weight. 1
If the amount is less than 50 parts by weight, a sufficient flame retarding effect cannot be obtained, and if the amount is more than 50 parts by weight, the heat resistance and impact resistance of the obtained composition are remarkably lowered, and the volatile content during molding is increased. And the like.

In the present invention, when higher flame retardancy is required, the above components (A) to (D) are further added with (E).
This can be achieved by adding at least one selected from silicone, fluorine resin, and phenol resin as a component. The silicone used in the present invention, in principle, has a

Embedded image There is no particular limitation as long as it has a skeleton. Examples of the silicone used in the present invention include polydimethylsiloxane, polymethylphenylsiloxane, amino-modified silicone, mercapto-modified silicone, and epoxy-modified silicone. These may be used alone or in combination of two or more. Furthermore, these silicones can be used in a wide range of molecular weights of several hundreds to several millions, and their forms are oily, varnish-like, gum-like,
It may be in any form such as resin. In the present invention, polydimethylsiloxane is preferably used.

The fluororesin used in the present invention is not particularly limited as long as it is a (co) polymer containing a fluorine atom. Examples of the fluorine-based resin used in the present invention include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-ethylene. Examples thereof include copolymers, polytrifluorochloroethylene, and polyvinylidene fluoride. These may be used alone or in combination of two or more. The fluorinated resin may be in any form such as emulsion, suspension, microfibril, powder and granule.
In the present invention, polytetrafluoroethylene is preferably used.

When silicone or a fluororesin is used in the present invention, the addition amount is (A) polycarbonate resin,
0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, relative to 100 parts by weight of the resin component consisting of the (B) graft copolymer and (C) (A) and a thermoplastic resin other than (B). Parts, more preferably 0.1 to 2 parts by weight, and particularly preferably 0.1 to 1 parts by weight. If the amount of silicone or fluorine-based resin is 0.01 parts by weight or less, a sufficient anti-dripping effect cannot be obtained, and if it exceeds 5 parts by weight, the appearance of the molded product of the resin composition blended is poor and the melt viscosity is increased. It may cause a phenomenon.

The phenolic resin used in the present invention is
It is obtained by reacting phenols and aldehydes under an acidic or alkaline catalyst. Phenols include phenol, cresol, xylenol, ethylfunol,
Propylphenol, butylphenol, amylphenol, nonylphenol, phenylphenol, phenoxyphenol, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) pentane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) butane, bis ( 4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide, dihydroxynaphthalene, bis (4-hydroxyphenyl) propane, and the like, and mixtures thereof.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, glyoxal and the like. Further, an aromatic monoaldehyde having at least one phenolic hydroxyl group in one molecule can also be used. Examples of such aromatic monoaldehydes include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, β-resorcylaldehyde and vanillin.

Examples of the ketones include acetone and the like. These aldehydes and / or ketones may be used alone or in combination of two or more.

In the present invention, both a resol type resin and a novolac type phenolic resin can be used, but a novolac type phenolic resin is preferably used. The novolac-type phenol resin used in the present invention is obtained by reacting the above-mentioned phenols with the above-mentioned aldehydes and / or ketones under an acid catalyst by a known method.
Further, in the present invention, a novolac type phenol resin obtained by substituting a part or all of the above aldehyde and / or ketone with dicyclopentadiene and reacting with the above phenol can also be used. Further, in the present invention, a novolac type phenol resin obtained by replacing a part or all of the aldehyde and / or ketone with an aralkyl halide and / or an aralkyl alcohol derivative and reacting with the phenol can be used. The aralkyl halide and / or aralkyl alcohol derivative in the present invention is represented by the general formula (II).

Embedded image (In the formula, R is a compound which is a halogen atom such as chlorine or bromine, a hydroxyl group, or an alkoxy group.) As the alkoxy group, a lower alkoxy group having 4 or less carbon atoms is preferable.
The aralkyl halide preferably used is α,
α'-dichloro-p-xylene, α, α'-dibromo-
P-xylene, α, α′-diiodo-p-xylene and the like can be mentioned, and preferable aralkyl alcohol derivatives are α, α′-dihydroxy-p-xylene and α, α′-dimethoxy-p-. Xylene, α, α '
-Diethoxy-p-xylene, α, α'-dipropoxy-p-xylene, α, α'-di-n-butoxy-p-xylene, α, α'-di-sec-butoxy-p-xylene, α, Examples include α'-di-isobutoxy-p-xylene.

When the phenolic resin is used in the present invention, the addition amount thereof is in the range of 1 to 30 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the resin component consisting of (A) to (C). is there. When the amount of the phenolic resin is less than 1 part by weight, the anti-dripping effect is not sufficiently obtained and the flame retardancy is poor, and when the amount exceeds 30 parts by weight, the light resistance and impact resistance of the obtained resin composition are remarkable. This is not preferable because it causes adverse effects such as deterioration.

In the present invention, silicone, fluororesin,
Both of the phenolic resin and the phenolic resin effectively act to prevent the resin from dripping during combustion, but when a flame-retardant resin composition having excellent light resistance is obtained, a fluororesin and / or
Alternatively, it is preferable to use silicone.

The flame-retardant resin composition of the present invention does not use a compound containing bromine or chlorine as a flame-retardant component,
Although it exhibits an excellent flame retardant effect, a commonly used known flame retardant additive may be used in combination. The flame retardant additive is not particularly limited as long as it has a flame retardant effect, chlorine or bromine-containing compounds, antimony compounds, nitrogen compounds, thermally expandable graphite, carboxylic acid metal salts, sulfonic acid metal salts, Flame retardant additives such as boric acid metal salt, metal oxide, metal hydroxide, ferrocene, guanamine resin, melamine resin and urea resin can be used. These flame retardant additives may be used alone or in combination of two or more.

There is no particular limitation on the method of mixing the resin and the flame retardant, and any means can be adopted as long as it can uniformly mix them. For example, mixing, kneading, and the like using various mixing machines such as an extruder, a Henschel mixer, a Banbury mixer, a kneader, and a heating roll can be appropriately adopted. At the time of kneading, each component may be kneaded at once, or any component may be kneaded and then the remaining components may be added and kneaded. A preferable kneading method is a method using an extruder, and a twin-screw extruder is particularly preferable as the extruder.

At this time, if necessary, various fillers, additives and the like can be added in an amount such that the effect is exhibited within the range of not impairing the flame retardancy. Examples thereof include glass fibers, asbestos, carbon fibers, aromatic polyamide fibers, potassium titanate whisker fibers, metal fibers, ceramic fibers, fibrous fillers such as boron whisker fibers, mica, silica, talc, clay, calcium carbonate, Glass beads,
Fillers such as glass balloons and glass flakes, release agents, lubricants, plasticizers, dispersants, UV absorbers, light stabilizers,
Examples thereof include additives such as antioxidants, heat resistance stabilizers, antioxidants, and dyes (face). Further, an impact strength improver for improving the properties of the polymer blend, a compatibilizing component and the like can be added.

[0038]

The present invention will be described below with reference to examples.
The present invention is not limited to these.
All parts and ratios described in the present specification are based on weight. The following are those used in the compounding formulations of Examples and Comparative Examples. Polycarbonate resin: Teijin Chemicals Panlite L-1250 Graft copolymer (1): Polybutadiene latex 8
A latex obtained by graft-copolymerizing 0 part (average particle size 320 mμ, solid content concentration 50%) with 18 parts acrylonitrile and 42 parts styrene was heated to 40 ° C., and then an aqueous calcium chloride solution was added to precipitate and wash with water. -Powder obtained by filtration and drying Graft copolymer (2): After raising the latex used in producing the graft copolymer (1) to 40 ° C, precipitation with magnesium sulfate aqueous solution, washing with water and filtration -Powder obtained by drying Graft copolymer (3): The latex used in producing the graft copolymer (1) was heated to 50 ° C, and then precipitated with an aqueous sulfuric acid solution, washed with water, filtered and dried. Powder obtained as a result Graft copolymer (4): obtained by heating the latex used in the production of graft copolymer (1) to 30 ° C., precipitating with an aqueous sulfuric acid solution, washing with water, filtering and drying. Grafted powder Body (5): The latex used for producing the graft copolymer (1) was precipitated at 20 ° C. with an aqueous solution of acetic acid / sulfuric acid mixture, washed with water, filtered, and hydrated powder was again slurried in pure water. Powdered copolymer (6) obtained by filtration and drying after being dispersed in ethylene, and 40 parts of ethylene / propylene rubber modified with maleic anhydride and an acrylonitrile / styrene copolymer having a glycidyl methacrylate residue (26 Pellets obtained by kneading 60 parts // 74 ratio) with a twin-screw extruder. Table 1 shows the results of analysis of impurities in the graft copolymer. The impurities in the graft copolymer were quantified by the following method. First, after carbonizing the sample with a low heat burner,
It was ashed by heating in an electric furnace at 00 ° C for 1 hour. Then, after dissolving the residue in a diluted nitric acid aqueous solution prepared by diluting concentrated nitric acid 50 times,
Atomic absorption spectrometer (Hitachi Z
6100 type), and calcium and magnesium are IC
It was quantified with a P emission spectrometer (ICP-575 manufactured by Jarrell).

[0039]

[Table 1]

Thermoplastic resin (1) other than (A) and (B): acrylonitrile / styrene (28/72 ratio)
A thermoplastic resin (2) other than the copolymers (A) and (B) obtained by suspension polymerization of the mixture: styrene / N-phenylmaleimide / maleic anhydride (47 / 52.5 /
Copolymer obtained by solution polymerization of mixture (0.5 ratio) (A) and thermoplastic resin other than (B) (3): terephthalate NEH2050 manufactured by Unitika Ltd. (A) and thermoplastic resin other than (B) (4) : Unitika Polyarylate U-100 Phosphorus Compound (1): Daihachi Chemical Industry Triphenyl Phosphate Phosphorus Compound (2): Daihachi Chemical Industry Resorcinol Bis (Diphenyl Phosphate) CR-733S Fluorine Resin: Mitsui DuPont Fluorochemical Polytetrafluoroethylene Teflon 6J Phenolic resin: Phenol novolac resin with softening point of 92 ° C Silicone: Toray Dow Corning Silicone polydimethylsiloxane SH-200 (viscosity 30000cs) Examples 1 to 15 and Comparative Examples 1 to 5 Tables 1 and 2 show the resins and compounds exemplified above.
Mixing and stirring with a Henschel mixer at the mixing ratio shown in, and a vented 30 mm φ twin-screw extruder (Ikegai Tekko KK, P
CM-30), melt kneading and extruding at 280 ° C.,
Pelletized with a pelletizer. After sufficiently drying the pellets thus obtained, a test piece was prepared by injection molding and evaluated. The results are shown in Tables 2 and 3. The evaluation method was as follows. Heat distortion temperature: Measured according to ASTM D648. (18.6Kg / cm ² ) Izod impact strength: 2 according to ASTM D256
It was measured at 3 ° C. using a 1/8 inch thick, notched test piece. Flame retardance: Based on the UL-94 test method, a test piece having a thickness of 1/16 inch was used for evaluation.

[0041]

[Table 2]

[0042]

[Table 3]

From Tables 2 and 3, by using the graft copolymer containing few impurities, good flame retardancy can be obtained even with the addition of a small amount of phosphorus compound, and the heat distortion temperature and Izod impact strength are also excellent. Flame-retardant resin is obtained. Further, by additionally using at least one selected from silicone, fluorine resin, and phenol resin, the heat distortion temperature and the Izud impact strength are less decreased,
Higher flame-retardant resin is obtained.

[0044]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a flame retardant resin composition having excellent flame retardancy, heat resistance and impact resistance, and having an excellent balance of physical properties. Further, it can be suitably used as applications such as electronic / electrical products and office automation equipment, and as materials for various parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 51/00 LKN C08L 51/00 LKN LKP LKP 61/06 LMT 61/06 LMT LMY LMY LNB LNB 83 / 04 LRS 83/04 LRS LRY LRY 101/00 LSY 101/00 LSY

Claims (2)

[Claims] 1. (A) Polycarbonate resin 1 to 99% by weight, (B) Graft copolymer 1 to 50% by weight, (C)
(D) Phosphorus compound 1 per 100 parts by weight of a resin component consisting of 0 to 98% by weight of a thermoplastic resin other than (A) and (B)
In a composition containing 50 to 50 parts by weight, the total concentration of sodium and potassium present in the graft copolymer is 2
00ppm or less and magnesium concentration of 150pp
A flame-retardant resin composition, wherein the flame retardant resin composition has m or less and a calcium concentration of 1000 ppm or less. 2. (A) Polycarbonate resin 1 to 99% by weight, (B) Graft copolymer 1 to 50% by weight, (C)
(D) Phosphorus compound 1 per 100 parts by weight of a resin component consisting of 0 to 98% by weight of a thermoplastic resin other than (A) and (B)
.About.50 parts by weight and (E) at least one selected from silicone, fluorine resin, and phenol resin.
In a composition containing 01 to 30 parts by weight, the total concentration of sodium and potassium present in the graft copolymer is 200 ppm or less, and the concentration of magnesium is 150.
A flame-retardant resin composition, which has a concentration of ppm or less and a calcium concentration of 1000 ppm or less.